CN115368529A - Epoxy-modified polyurethane resin, preparation method thereof, photocuring composition containing epoxy-modified polyurethane resin and application of photocuring composition - Google Patents
Epoxy-modified polyurethane resin, preparation method thereof, photocuring composition containing epoxy-modified polyurethane resin and application of photocuring composition Download PDFInfo
- Publication number
- CN115368529A CN115368529A CN202110535369.2A CN202110535369A CN115368529A CN 115368529 A CN115368529 A CN 115368529A CN 202110535369 A CN202110535369 A CN 202110535369A CN 115368529 A CN115368529 A CN 115368529A
- Authority
- CN
- China
- Prior art keywords
- polyurethane resin
- epoxy
- substituted
- modified polyurethane
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000016 photochemical curing Methods 0.000 title abstract description 8
- -1 oxetane compound Chemical class 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 125000002091 cationic group Chemical group 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 125
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 150000002009 diols Chemical class 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical group 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000012954 diazonium Substances 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229960000834 vinyl ether Drugs 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 2
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 claims description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 2
- UYCGHYYLNBVUGK-UHFFFAOYSA-N 4-(ethenoxymethyl)-1,3-dioxolan-2-one Chemical compound C=COCC1COC(=O)O1 UYCGHYYLNBVUGK-UHFFFAOYSA-N 0.000 claims description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000012974 tin catalyst Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 35
- 238000010438 heat treatment Methods 0.000 description 12
- 238000004321 preservation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- WREOTYWODABZMH-DTZQCDIJSA-N [[(2r,3s,4r,5r)-3,4-dihydroxy-5-[2-oxo-4-(2-phenylethoxyamino)pyrimidin-1-yl]oxolan-2-yl]methoxy-hydroxyphosphoryl] phosphono hydrogen phosphate Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O[C@H]1N(C=C\1)C(=O)NC/1=N\OCCC1=CC=CC=C1 WREOTYWODABZMH-DTZQCDIJSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940125758 compound 15 Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- VQVGJEIVVJBMCV-UHFFFAOYSA-N (4-octoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 VQVGJEIVVJBMCV-UHFFFAOYSA-N 0.000 description 1
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
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- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSLNIWYKWMVUMK-UHFFFAOYSA-N [N+]=1(NC=CC=1)[N+]#N Chemical compound [N+]=1(NC=CC=1)[N+]#N XSLNIWYKWMVUMK-UHFFFAOYSA-N 0.000 description 1
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- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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Abstract
The invention provides epoxy modified polyurethane resin and a preparation method thereof, a photocuring composition containing the same and application thereof. An epoxy-modified polyurethane resin comprising a polyurethane resin body and at least one oxetane compound attached to the end of the molecular chain of the polyurethane resin body by chemical grafting; wherein the oxetane compound is an oxetane compound containing active hydrogen functional groups, and the active hydrogen functional groups comprise one or more of hydroxyl, carboxyl and amino; the polyurethane resin body has the following structure. After the epoxy modified polyurethane resin is applied to a cationic curing system, a cured resin film layer has excellent performances such as high adhesion, high wear resistance and high toughness, and the application range of the cationic curing system is greatly expanded.
Description
Technical Field
The invention relates to the field of energy-curable, in particular to epoxy modified polyurethane resin, a preparation method thereof, a photocuring composition containing the same and application thereof.
Background
In the light-cured composition, the film-forming resin is a light-sensitive resin with relatively low molecular weight, the relative molecular weight is generally hundreds to tens of thousands, and the film-forming resin is one of the components with the largest proportion in a light-cured product and accounts for more than 40 percent of the mass of the whole formula; the properties of the film-forming resin substantially determine the properties of the cured material, such as the hardness of the cured film layer, adhesion to the substrate, flatness and gloss of the film layer, and the like. The existing commonly used film-forming resin is mainly acrylic acid (ester) mainly cured by free radical light, and has the advantages of cheap raw materials, wide sources and more product types, a plurality of series of acrylic acid (ester) resins with different properties, such as polyurethane acrylate, are derived by modification, and as a more researched UV curing resin, because the molecules of the resin contain urethane bonds, a plurality of hydrogen bonds can be formed among chains, so that the film has very excellent friction resistance and flexibility, and simultaneously has good chemical resistance.
After the film-forming resin is prepared into a photocurable composition, the film-forming resin can be classified into a radical curing system, a cationic curing system, and the like according to the curing type. However, the radical curing system has inevitable disadvantages such as skin irritation, insufficient curing due to oxygen inhibition, or complicated process due to oxygen removal or barrier treatment required for curing. In recent years, cationic photopolymerizable compositions have been receiving increasing attention because of their advantages such as low skin irritation and no need for a simple oxygen barrier treatment process during curing, but cationic curable monomer resins are limited in kind and mainly include low molecular weight resins having epoxy groups or vinyl ether groups, and urethane acrylates are not suitable. Meanwhile, the cation curing system has high crosslinking density and high strength of the cured film layer, but has poor toughness. The above reasons all greatly limit the application of cationic photocuring.
For the above reasons, there is a need for modification studies of polyurethanes to make them more suitable for application in photocurable compositions of cationically curable systems and to improve the abrasion resistance and flexibility of the cured coatings.
Disclosure of Invention
The invention mainly aims to provide an epoxy modified polyurethane resin, a preparation method thereof, a photocuring composition containing the same and application thereof, and aims to solve the problems that the polyurethane resin is not suitable for a cationic curing system in the prior art, and a film layer cured by the conventional cationic curing system is poor in friction resistance and flexibility.
In order to achieve the above object, according to one aspect of the present invention, there is provided an epoxy-modified polyurethane resin comprising a polyurethane resin body and at least one oxetane compound attached to the molecular chain end of the polyurethane resin body by chemical grafting; wherein the oxetane compound is an oxetane compound containing active hydrogen functional groups, and the active hydrogen functional groups comprise one or more of hydroxyl, carboxyl and amino; the polyurethane resin body has a structure shown in a general formula I:
in the general formula I, M represents a substituted or unsubstituted divalent alkyl group, and-CH therein 2 -optionally substituted by carbonyl; r 1 Represents a substituted or unsubstituted divalent aryl group, a substituted or unsubstituted divalent cycloalkyl group, a substituted or unsubstituted divalent straight-chain alkyl group; n is an integer of 1 to 8.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing the above epoxy-modified polyurethane resin, comprising the steps of: providing a polyurethane resin body with a structure shown in a general formula I; and carrying out grafting reaction on the polyurethane resin body and an oxetane compound to obtain the epoxy modified polyurethane resin.
According to another aspect of the present invention, there is provided a curable resin composition comprising the above epoxy-modified polyurethane resin and an initiator.
According to a further aspect of the present invention there is provided the use of an epoxy-modified polyurethane resin as described above or a curable composition as described above in an energy curable article, wherein the energy curable article is an ink, a coating or an adhesive.
The invention provides epoxy modified polyurethane resin, which is characterized in that at least one oxetane compound is introduced into the tail end of a polyurethane resin bulk molecular chain shown in a general formula I in a chemical grafting mode, so that the epoxy modified polyurethane resin can be suitable for a cationic curing system. Correspondingly, after the cationic curing agent is applied to a cationic curing system, the cured resin film layer has excellent performances such as high adhesive force, high wear resistance and high toughness, and the application range of the cationic curing system is greatly expanded.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In the disclosure of the present invention, the related terms have meanings commonly understood in the art unless otherwise specified. The numerical range includes the end points and all points between the end points, e.g. "C 1 -C 10 "comprises C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 The "integer of 1 to 4" includes 1, 2, 3 and 4.
As described in the background section, the prior art urethane acrylates are not suitable for cationic curing systems, and the prior art cationic curing systems have poor abrasion resistance and flexibility of the cured film layer, although they have high crosslinking density, good compactness and small shrinkage.
In order to solve the above problems, the present invention provides an epoxy-modified polyurethane resin, characterized in that the epoxy-modified polyurethane resin comprises a polyurethane resin body and at least one oxetane compound attached to the molecular chain end of the polyurethane resin body by chemical grafting; wherein the oxetane compound is an oxetane compound containing active hydrogen functional groups, and the active hydrogen functional groups comprise one or more of hydroxyl, carboxyl and amino; the polyurethane resin body has a structure shown in a general formula I:
in the general formula I, M represents a substituted or unsubstituted divalent alkyl group, and-CH therein 2 -optionally (optional) interrupted by a carbonyl group; r 1 Represents a substituted or unsubstituted divalent aryl group, a substituted or unsubstituted divalent cycloalkyl group, a substituted or unsubstituted divalent straight-chain alkyl group; n is an integer of 1 to 8.
At least one oxetane compound is introduced into the tail end of the polyurethane resin bulk molecular chain shown in the general formula I in a chemical grafting mode, so that the polyurethane resin bulk molecular chain can be suitable for a cationic curing system. Correspondingly, after the cationic curing agent is applied to a cationic curing system, the cured resin film layer has excellent performances such as high adhesive force, high wear resistance and high toughness, and the application range of the cationic curing system is greatly expanded.
In a word, the epoxy modified polyurethane resin enriches the types of the resin of the cationic curing system and provides more choices for improving the wear resistance and flexibility of the cationic curing coating.
In a preferred embodiment, the active hydrogen functional groups are hydroxyl groups. Compared with other active hydrogen functional groups, the oxetane compound with hydroxyl is selected, and the grafting effect is better in the preparation process. Preferably, the oxetane compound has the structure shown in formula II:
in the general formula II, R 2 Is represented by C 1 -C 40 Linear or branched m-valent alkyl of (2), C 2 -C 20 M-valent alkenyl of (A), C 6 -C 40 M-valent aryl of (a), wherein-CH 2 Optionally substituted by-O-, -NH-),
A carbonyl group,
Substituted, and two-O-are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be substituted by alkyl, halogen or nitro; r 3 Is represented by C 1 -C 20 Linear or branched alkylene of (a) with-CH in the main chain 2 -is optionally-O-or
Substituted, and the two-O-are not directly connected; and optionally, in the presence of a catalyst, one or more hydrogen atoms in the group may each independently be replaced by alkyl, halogen,Nitro or
Substitution; r 4 Represents hydrogen, halogen, nitro, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 4 -C 20 Alkylcycloalkyl of (A), C 2 -C 10 Alkenyl or C 6 -C 20 Optionally, one or more hydrogen atoms in the group may each independently be substituted with alkyl, halogen, or nitro; m represents an integer of 1 to 8.
The oxetane compound of the formula II is selected, so that on one hand, the molecular weight is more suitable, and the grafting efficiency is better in the grafting process. On the other hand, the modified polyurethane resin can be better mixed with other components in a cation curing system, so that the adhesive force, the wear resistance and the flexibility of a cured resin film layer are improved, and better comprehensive performance is considered.
More preferably, represents C 1 -C 40 Linear or branched m-valent alkyl of (2), C 2 -C 10 Linear or branched m-valent alkenyl of (A), C 6 -C 30 M-valent aryl of (a), wherein-CH 2 -is optionally substituted by-O-, -NH-or
Substituted, and the two-O-are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be substituted with alkyl, halogen, or nitro. Above R 2 The introduction of the group can better promote the cationic curing performance of the epoxy modified polyurethane resin.
Illustratively, R 2 Including but not limited to the following structures: c 1 -C 12 Linear or branched 1-4 valent alkyl, C 2 -C 6 A straight or branched chain alkenyl group having a valence of 1 to 4,
CH 3 -O-CH 2 CH 2 *、
*CH 2 CH 2 NHCH 2 CH 2 *、
In order to further improve the cationic curability of the epoxy-modified polyurethane resin, in a preferred embodiment, R 3 Is represented by C 1 -C 10 Linear or branched alkylene of (a) with-CH in the main chain 2 -is optionally-O-or
Substituted, and the two-O-are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be substituted by alkyl or
Substitution; more preferably, R 3 Is represented by C 1 -C 6 Linear or branched alkylene of (a) with-CH in the main chain 2 -is optionally substituted by-O-, and two-O-are not directly connected.
More preferably, R 4 Represents hydrogen, C 1 -C 10 Straight or branched alkyl of (2), C 3 -C 10 Cycloalkyl of, C 4 -C 10 Cycloalkylalkyl of (C) 4 -C 10 Alkylcycloalkyl of (A), C 2 -C 8 Alkenyl or phenyl of (a); more preferably, R 4 Is represented by C 1 -C 4 Straight or branched alkyl of, or C 4 -C 8 Cycloalkylalkyl of (1).
In a preferred embodiment, m is preferably an integer from 1 to 6, more preferably an integer from 1 to 4.
Illustratively, the oxetane compound is selected from one or more of the following compounds:
the oxetane compound modified polyurethane resin can better balance the cationic curing performance of the resin, the compatibility with other components, the flexibility after film forming, the wear resistance and the like, so that the modified polyurethane resin has better and excellent application performance.
M and R in the polyurethane resin body of the general formula 1 The substituent structures commonly used in polyurethane resins in the field of film-forming resins can be selected, and in a preferred embodiment, M represents C 2 -C 100 Straight or branched alkylene of (2), wherein-CH 2 -is optionally substituted by-O-or-COO-; more preferably, M represents a residue formed by removing a terminal hydroxyl group from a polyether diol or a polyester diol, or by ring-opening via a terminal epoxy group and removing-O-; more preferably, the polyether glycol is polyethylene glycol (PEG 300, PEG500PEG1000, PEG2000, PEG4000, etc.), polypropylene glycol (specifically, PPG200, PPG400, PPG1000, PPG2000, PPG4000, etc.), ethylene oxide-propylene oxide copolymerA copolymer or polytetrahydrofuran diol (PTMEG 1000, PTMEG2000, etc.), wherein the polyester diol is a polyester diol (POL-3112, POL-356, POL-345, POL-338, POL-328, POL-23112, POL-2375, POL-2365, POL-7356, POL-2112, POL-256, POL-2476, POL-2500, etc.) or a polycaprolactone diol (PCL-205, PCL-208, PCL-210, PCL-212, PCL-220, etc.); preferably, R 1 Is represented by C 6 -C 18 Substituted or unsubstituted divalent aryl radical of (A), C 5 -C 18 Substituted or unsubstituted divalent cycloalkyl radical of (1), C 2 -C 10 Substituted or unsubstituted divalent straight-chain alkyl group of (a); more preferably, R 1 Denotes the residue formed after removal of the-NCO group of the diisocyanate; further preferably, the diisocyanate is 2,4-TDI, 2,6-TDI, MDI, m-XDI, p-XDI, HDI, IPDI or HMDI.
Selecting the above M and R 1 The polyurethane resin body shown in the general formula I is formed, the polyurethane resin body has better flexibility, wear resistance and adhesion performance, and after the polyurethane resin body is applied to a cation curing system through epoxy modification, the overall performance of a resin film layer is better. Meanwhile, the polyurethane resin has better film-forming property of the main molecular chain, is convenient to process, and has better processing property after being applied to a cation curing system.
According to another aspect of the present invention, there is also provided a method for preparing the epoxy-modified polyurethane resin, comprising the steps of: providing a polyurethane resin body with a structure shown in a general formula I; and carrying out grafting reaction on the polyurethane resin body and an oxetane compound to obtain the epoxy modified polyurethane resin. Through the grafting reaction, the-NCO at the tail end of the molecular chain of the polyurethane resin body can react with the active hydrogen functional group in the oxetane compound to complete the chemical grafting of the oxetane compound.
The polyurethane resin body can be prepared by the method commonly used in polyurethane synthesis reaction, and in a preferred embodiment, the polyurethane resin body is prepared by the following method: isocyanate is used as a first raw material, polyether diol or polyester diol is used as a second raw material, the first raw material and the second raw material are mixed, and the excess of-NCO in the mixed raw materials is controlledAnd (4) performing polymerization reaction under the action of a catalyst to obtain a polyurethane resin body. In the process, the specific structure of the isocyanate, the polyether diol or the polyester diol can be according to R in the general formula I 1 And M structure, as will be understood by those skilled in the art, are not described in detail herein.
Preferably, the molar ratio of-NCO to-OH in the raw materials is (1.1-2): 1, so that the prepared polyurethane resin still carries part of unreacted-NCO at the molecular chain terminal, thereby facilitating the subsequent grafting reaction.
To further increase the polymerization efficiency, in a preferred embodiment, the catalyst includes, but is not limited to, amine-based catalysts and/or organometallic catalysts; more preferably, the amine catalyst is one or more selected from the group consisting of N, N-dimethylcyclohexylamine, triethylamine, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, triethanolamine and N, N' -dimethylpyridine, and the organometallic catalyst is an organotin catalyst, and more preferably dibutyltin dilaurate.
Preferably, the catalyst is used in an amount of 0.01 to 1% by weight based on the isocyanate; preferably, the reaction temperature for the polymerization reaction is 30 to 120 ℃. At this catalyst level and temperature, the grafting efficiency is higher. In the actual operation process, the specific reaction time can be adjusted according to the dosage of the catalyst, the viscosity change of the polymerization reaction system and the like, and the reaction time is preferably controlled to be 3-5h.
As previously mentioned, the isocyanate as the first starting material may be according to the specific structure of R in formula I 1 Adjusting the structure of the substituent group; polyether diol or polyester diol is used as the second raw material, and the specific structure of the polyether diol or polyester diol can be adjusted according to the structure of the M substituent group in the general formula I. In a preferred embodiment, the isocyanate is 2,4-TDI, 2,6-TDI, MDI, m-XDI, p-XDI, HDI, IPDI or HMDI; the polyether diol is polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer or polytetrahydrofuran diol, and the polyester diol is polyester diol or polycaprolactone diol. The polyurethane resin prepared by the isocyanate, the polyether diol or the polyester diol through polymerization reaction is modified by epoxyThe coating has better application performance and better promotion effect on the processing of a cationic curing system and the performance of a film-forming coating.
In order to graft the oxetane compound more sufficiently, in a preferred embodiment, the active hydrogen functional group in the oxetane compound is excessive to the unreacted — NCO in the polyurethane resin bulk during the above-mentioned grafting reaction; preferably, the molar ratio of active hydrogen functional groups in the oxetane compound to unreacted-NCO in the polyurethane resin bulk is (1.1-2): 1. More preferably, the reaction temperature during the grafting reaction is 50-80 ℃. In the actual synthesis process, whether the reaction is finished or not can be determined according to the conversion rate of-NCO in a reaction system, the reaction time can be controlled to be 3-4 h usually, the conversion rate of NCO is detected by sampling to be more than 98%, and the reaction is finished.
The above oxetane compounds are prepared by methods known in the art and will not be described herein.
According to still another aspect of the present invention, there is also provided a curable resin composition comprising the above epoxy-modified polyurethane resin and an initiator. By using the epoxy modified polyurethane resin, a resin film layer formed by initiating a curing reaction of the curable resin composition by an initiator has higher adhesive force, good weather resistance and flexibility, and also has the advantage of high hardness.
In a preferred embodiment, the initiator is a cationic initiator. As described hereinbefore, the cationic curability of the polyurethane resin is improved precisely by using the above epoxy-modified polyurethane resin. Preferably, the above cationic initiators include, but are not limited to, one or more of diazonium salts, onium salts, and organometallic complexes.
Illustratively, the cationic initiator is one or more of diazonium fluoroborate, pyrazolium diazonium inner salt, triptycene diazonium salt, diazoaminobenzene, triaryl sulfonium hexafluorophosphate, triaryl sulfonium antimonate, 4' -dimethyl diphenyl iodonium hexafluorophosphate, 4' -dimethyl diphenyl iodonium hexafluorophosphate, 10- (4-biphenyl) -2-isopropyl thioxanthone-10-sulfonium hexafluorophosphate, 4-octyloxy diphenyl iodonium hexafluoroantimonate, bis (4-tert-butyl-phenyl) iodonium hexafluorophosphate, diphenyl- (4-phenyl sulfide) phenyl sulfonium hexafluorophosphate, bis (4-diphenyl thiophenyl) sulfide dihexafluoroantimonate, 4-isobutylphenyl-4 ' -methylphenyl iodonium hexafluorophosphate, 6-isopropylbenzene cyclopentadienyl iron hexafluorophosphate.
To further improve the overall application properties of the curable composition, in a preferred embodiment, the curable composition further comprises a cationically polymerizable compound; preferably, the cation polymerizable compound includes one or more of epoxy compounds and vinyl ether compounds; more preferably, the epoxy compound is selected from one or more of bisphenol A epoxy resin, aliphatic glycidyl ether resin, aliphatic epoxy resin and oxetane compound, and the vinyl ether compound is selected from one or more of triethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether and dodecyl vinyl ether.
In order to provide the composition comprising the epoxy-modified polyurethane resin with better application performance, in a preferred embodiment, the composition further comprises an auxiliary agent; preferably, the auxiliary agent is one or more of a drier, a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a mold release agent, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a colorant, a stabilizer, a release agent, an antistatic agent, a pigment, a dye, and a flame retardant.
In practice, the content of the epoxy-modified polyurethane resin is preferably controlled to 10 to 80% by weight of the entire curable composition, and the contents of the rest of the initiator, the auxiliary agent, and the cationically polymerizable monomer may be adjusted.
To more fully cure the composition, in a preferred embodiment, the composition is cured by at least one of light, heat, or electron radiation; preferably, the composition is cured by UV light. The UV light source may be a light source or radiation source made to emit light in the ultraviolet range (i.e. between 10nm and 420 nm), and may for example be selected from: fluorescent lamps, fluorescent black light lamps, short wave ultraviolet lamps, lasers, ultraviolet gas lasers, high power gas lasers (e.g., nitrogen lasers or excimer lasers), ultraviolet laser diodes, ultraviolet solid state lasers, electron beams, illuminators, monochromatic light sources, light Emitting Diodes (LEDs), LED arrays, ultraviolet LEDs, gas discharge lamps, argon and deuterium lamps, hg-Cd lamps, arc lamps, flash lamps, xe or halogen lamps, or any other suitable light source.
According to yet another aspect of the present invention, there is also provided a use of the epoxy-modified polyurethane resin or the curable composition described above in an energy curable article, wherein the energy curable article is an ink, a coating or an adhesive. By way of example, the inks may be listed: relief, intaglio, lithographic and mesh inks; the coating materials include: building coatings, anticorrosive coatings, automotive coatings, dew-proof coatings, antirust coatings, waterproof coatings, moisture-retaining coatings, elastic coatings; the adhesive may be exemplified by: solvent-based adhesives, emulsion-based adhesives, reactive (thermosetting, UV-curing, moisture-curing) adhesives, hot-melt adhesives, remoistenable adhesives, pressure-sensitive adhesives.
As used herein, unless otherwise defined, the term "energy curable" means crosslinked (i.e., cured) upon exposure to radiation, such as actinic radiation, particularly UV or electron beam radiation, or thermal radiation.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation of Compound A (Compounds 1-4, 6, 9, 10, 11, 15)
Preparation of Compound 1
Adding 16g (0.5 mol) of methanol, 4g (0.1 mol) of sodium hydroxide and 100g of toluene into a three-neck flask in sequence, stirring and heating to 80 ℃, dropwise adding 86g (0.5 mol) of 3-ethyl-3- [ (ethylene oxide-2-methoxy) methyl ] oxetane, continuing stirring and reacting after 1.5h of dropwise addition, keeping track of a gas phase until the content of the methanol is not changed, stopping heating, adjusting the pH to be neutral, filtering, washing with water, extracting, and evaporating the solvent under reduced pressure to obtain 102g of compound 15.
Preparation of Compound 2
58g (0.5 mol) of 3-hydroxymethyl-3-ethyloxetane, 4g (0.1 mol) of sodium hydroxide and 100g of toluene are sequentially added into a three-neck flask, the mixture is stirred and heated to 80 ℃, 86g (0.5 mol) of 3-ethyl-3- [ (ethylene oxide-2-methoxy) methyl ] oxetane is added dropwise after 1.5h of dropwise addition, the stirring reaction is continued, the gas phase is tracked until the content of the 3-hydroxymethyl-3-ethyloxetane is not changed, the heating is stopped, the pH is adjusted to be neutral, and 130g of compound 2 is obtained by filtering, washing with water, extracting and evaporating the solvent under reduced pressure.
Referring to the preparation methods of compounds 1 and 2, compounds 1, 3, 4, 6, 9, 10, 11, 15 were prepared.
Preparation of epoxy-modified polyurethane resin (1-15)
Example 1:
42g (0.25 mol) of HDI and 0.06g of dibutyltin dilaurate are put into a four-neck flask, uniformly stirred, heated to 45 ℃,170g (0.17 mol) of PPG1000 is dripped into a reaction flask at a constant pressure dropping funnel at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, dripping is completed within 2h, and the temperature is raised to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. 34.7g of compound 15 (0.17 mol) is weighed and placed in a constant pressure dropping funnel, dropwise adding is carried out at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise adding is completed within 2 hours, and the temperature is increased to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, so that resin 1 is obtained.
Example 2:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are added into a four-mouth flask, the mixture is uniformly stirred, the temperature is increased to 45 ℃,170g (0.17 mol) of PPG1000 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is completed within 2h, the temperature is increased to 55 ℃, and the heat preservation reaction is carried out until the NCO conversion rate is not changed any more. Weighing 37.1g of compound 1 (0.17 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, and obtaining resin 2.
Example 3:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are added into a four-mouth flask, the mixture is stirred uniformly, the temperature is increased to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction bottle at a constant speed through a constant pressure dripping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is completed within 2h, the temperature is increased to 55 ℃, and the reaction is kept at the temperature until the NCO conversion rate is not changed any more. 53.7g of compound 15 (0.263 mol) is weighed and placed in a constant pressure dropping funnel, dropwise added at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise addition is completed within 2h, and the temperature is increased to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, so that resin 3 is obtained.
Example 4:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are added into a four-mouth flask, the mixture is stirred uniformly, the temperature is raised to 45 ℃, 62.5g (0.0625 mol) of PPG1000 and 125g (0.0625 mol) of PPG2000 are weighed and mixed uniformly in a constant pressure dropping funnel, the mixture is dripped into a reaction bottle at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished within 2 hours, the temperature is raised to 55 ℃, and the reaction is kept at the temperature until the NCO conversion rate is not changed any more. 75.7g of compound 2 (0.263 mol) is weighed and placed in a constant pressure dropping funnel, dropwise adding is carried out at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise adding is completed within 2 hours, and the temperature is increased to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, so that resin 4 is obtained.
Example 5:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is heated to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. Weighing 76.5g of compound 1 (0.263 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining the resin 5.
Example 6:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, evenly stirred, heated to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction flask at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, dripping is finished for 2h, and heated to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. 75.6g of compound 2 (0.263 mol) is weighed and placed in a constant pressure dropping funnel, dropwise adding is carried out at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise adding is completed within 2 hours, and the temperature is increased to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, so that the resin 6 is obtained.
Example 7:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,170g (0.17 mol) of PPG1000 and a constant-pressure dropping funnel are dripped into a reaction bottle at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is raised to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. Weighing 48.4g of compound 2 (0.17 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining resin 7.
Example 8:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,170g (0.125 mol) of POL3112 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is heated to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. 60.5g of compound 3 (0.131 mol) is weighed and placed in a constant pressure dropping funnel, dropwise adding is carried out at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise adding is completed within 2 hours, the temperature is increased to 65 ℃ for reaction, and the resin 8 is obtained until the conversion rate of NCO is more than 98%.
Example 9:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is heated to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. Weighing 74.9g of compound 4 (0.131 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining the resin 9.
Example 10:
62.5g (0.25 mol) of MDI and 0.06g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is heated to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. Weighing 55.0g of compound 6 (0.131 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, and obtaining the resin 10.
Example 11:
65.5g (0.25 mol) of HMDI and 0.06g of dibutyltin dilaurate are added into a four-mouth flask, the mixture is stirred uniformly, the temperature is increased to 45 ℃,125g (0.125 mol) of POL3112 is added into a reaction bottle through a constant-pressure dropping funnel at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, the dropwise addition is completed within 2h, the temperature is increased to 55 ℃, and the reaction is kept at the temperature until the NCO conversion rate is not changed any more. Weighing 55.0g of compound 6 (0.131 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, and obtaining the resin 11.
Example 12:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are put into a four-mouth flask, the mixture is stirred uniformly, the temperature is raised to 45 ℃,170g (0.17 mol) of PTMEG1000 is dripped into a reaction bottle at a constant speed by a constant pressure dropping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is completed within 2 hours, the temperature is raised to 55 ℃, and the reaction is kept until the NCO conversion rate is not changed any more. 37.1g of the compound 1 (0.17 mol) is weighed and placed in a constant pressure dropping funnel, dropwise adding is carried out at a constant speed, the reaction temperature is controlled not to exceed 60 ℃, dropwise adding is completed within 2 hours, the temperature is increased to 65 ℃ for reaction, and the resin 12 is obtained until the conversion rate of NCO is more than 98%.
Example 13:
47g (0.25 mol) of XDI and 0.13g of dibutyltin dilaurate are put into a four-mouth flask, stirred uniformly, heated to 45 ℃,340g (0.17 mol) of PPG2000 is dripped into a reaction bottle at a constant pressure dropping funnel at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, the dripping is finished for 2h, and the temperature is raised to 55 ℃ for heat preservation reaction until the NCO conversion rate is not changed any more. Weighing 58.3g of compound 9 (0.084 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining the resin 13.
Example 14:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are put into a four-mouth flask, the mixture is stirred uniformly, the temperature is raised to 45 ℃,125g (0.125 mol) of POL3112 is dripped into a reaction flask at a constant speed through a constant pressure dripping funnel, the reaction temperature is controlled not to exceed 50 ℃, the dripping is completed within 2h, the temperature is raised to 55 ℃, and the temperature is kept for reaction until the NCO conversion rate is not changed any more. Weighing 56.9g of compound 10 (0.0875 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining the resin 14.
Example 15:
42.5g (0.25 mol) of TDI and 0.13g of dibutyltin dilaurate are put into a four-mouth flask, the mixture is uniformly stirred, the temperature is raised to 45 ℃,125g (0.125 mol) of PCL210 is dripped into a reaction flask at a constant pressure dropping funnel at a constant speed, the reaction temperature is controlled not to exceed 50 ℃, the dripping is completed within 2h, the temperature is raised to 55 ℃, and the temperature is kept for reaction until the NCO conversion rate is not changed any more. Weighing 64.1g of compound 11 (0.263 mol) in a constant-pressure dropping funnel, dropwise adding at a constant speed, controlling the reaction temperature to be not more than 60 ℃, completing dropwise adding for 2h, and heating to 65 ℃ for reaction until the conversion rate of NCO is more than 98%, thereby obtaining the resin 15.
Performance test
The application properties of the epoxy-modified polyurethane resin of the present invention, including the speed of curing, the adhesion of the cured coating, hardness, flexibility, and abrasion resistance, were evaluated by formulating an exemplary curable resin composition and comparing it with a composition without the addition of such a polyurethane resin and with the addition of other epoxy resins.
The raw materials were mixed uniformly in a dark room according to the formulation shown in Table 1 to obtain a photocurable composition. Unless otherwise indicated, the parts indicated are parts by mass.
TABLE 1
The sample performance testing operation was as follows:
the tinplate is used as a substrate, oil stains on the tinplate sheet are wiped off by acetone, the composition formula is coated on the tinplate substrate by a 20# wire bar in a yellow room, the coating thickness is about 15 mu m, and after curing, the tinplate substrate is baked at 120 ℃ for 30min for performance test.
The test method comprises the following steps:
(1) Curing speed: a crawler-type mercury lamp exposure machine is adopted, the maximum linear speed for achieving surface drying is calculated as the curing speed, the unit is m/min, the surface drying test method is carried out according to the regulation of national standard GB/T1728-1979, and the surface drying method adopts a method B.
(2) And (3) testing the adhesive force: the test results are shown in Table 2, with reference to the provisions of the national standard GB/T9286-1998. The larger the number, the worst the adhesion, and grade 0 represents the best adhesion.
(3) And (3) testing hardness: the test results are shown in Table 2 by referring to the regulations of the national standard GB/T6739-86.
(4) And (3) flexibility testing: the test results are shown in Table 2, which is carried out according to the regulations of the national standard GB/T30791-2014. The larger the number, the poorer the flexibility, 0T representing the best flexibility.
(5) And (3) testing the wear resistance: cutting a 5cm multiplied by 10cm sample by using a Model 339 abrasion resistance tester, fixing the sample on an abrasion resistance tester platform, scrubbing the surface of the hardened layer by using a #0000 steel wire wool and a load of 500g, and recording the times of scratches on the surface of the film after the surface is scrubbed, wherein the times are abrasion resistance times. The more the number of wear-resistance times, the higher (good) the wear-resistance, the test results are shown in table 2.
TABLE 2
As can be seen from Table 2, the epoxy modified polyurethane resin of the present invention has significantly improved flexibility and wear resistance of the composition, and can effectively improve the comprehensive performance of the cationic composition coating.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. The epoxy modified polyurethane resin is characterized by comprising a polyurethane resin body and at least one oxetane compound connected to the tail end of a molecular chain of the polyurethane resin body in a chemical grafting manner; wherein the oxetane compound is an oxetane compound containing active hydrogen functional groups, and the active hydrogen functional groups comprise one or more of hydroxyl, carboxyl and amino; the polyurethane resin body has a structure shown in a general formula I:
in the general formula I, the compound has the following structure,
m represents a substituted or unsubstituted divalent alkyl group, and wherein-CH 2 -optionally substituted by carbonyl;
R 1 represents a substituted or unsubstituted divalent aryl group, a substituted or unsubstituted divalent cycloalkyl group, a substituted or unsubstituted divalent straight-chain alkyl group;
n is an integer of 1 to 8.
2. The epoxy-modified polyurethane resin of claim 1, wherein the active hydrogen functional groups are hydroxyl groups; preferably, the oxetane compound has the structure shown in formula II:
in the general formula II, the compound is shown in the specification,
R 2 is represented by C 1 -C 40 Linear or branched m-valent alkyl of (C) 2 -C 20 M-valent alkenyl of, C 6 -C 40 M-valent aryl of (a), wherein-CH 2 Optionally substituted by-O-, -NH-,
a carbonyl group,
Substituted, and two-O-are not directly connected; and areAnd optionally, one or more hydrogen atoms in the group may each independently be substituted with alkyl, halogen, or nitro;
R 3 is represented by C 1 -C 20 Straight or branched alkylene of (2), of which the main chain has-CH 2 -is optionally-O-or
Substituted, and the two-O-are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be replaced by alkyl, halogen, nitro or
Substitution;
R 4 represents hydrogen, halogen, nitro, C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 4 -C 20 Cycloalkylalkyl of (C) 4 -C 20 Alkylcycloalkyl of (A), C 2 -C 10 Alkenyl or C 6 -C 20 Optionally, one or more hydrogen atoms in the group may each independently be substituted with alkyl, halogen, or nitro;
m represents an integer of 1 to 8.
3. The epoxy-modified polyurethane resin of claim 2, wherein R is R 2 Is represented by C 1 -C 30 Linear or branched m-valent alkyl of (C) 2 -C 10 Linear or branched m-valent alkenyl of (A), C 6 -C 30 M-valent aryl of (a), wherein-CH 2 Optionally by-O-, -NH-or
Substituted, and the two-O-are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be substituted with alkyl, halogen, or nitro;
preferably, R 2 Selected from the following structures:
C 1 -C 12 linear or branched 1-4 valent alkyl, C 2 -C 6 A straight-chain or branched 1-to 4-valent alkenyl group,
4. The epoxy-modified polyurethane resin according to claim 2 or 3, wherein R is 3 Is represented by C 1 -C 10 Linear or branched alkylene of (a) with-CH in the main chain 2 -is optionally-O-or
Substituted, and the two-O-groups are not directly connected; and optionally, one or more hydrogen atoms in the group may each independently be substituted by alkyl or
Substitution; more preferably, R 3 Is represented by C 1 -C 6 Linear or branched alkylene of (a) with-CH in the main chain 2 -is optionally substituted by-O-, and the two-O-are not directly connected.
5. The epoxy-modified polyurethane resin according to any one of claims 2 to 4, wherein R is R 4 Represents hydrogen, C 1 -C 10 Straight or branched alkyl of (2), C 3 -C 10 Cycloalkyl of, C 4 -C 10 Cycloalkylalkyl of (C) 4 -C 10 Alkylcycloalkyl of (A), C 2 -C 8 Alkenyl or phenyl of (a); more preferably, R 4 Is represented by C 1 -C 4 Or C is a straight or branched alkyl group 4 -C 8 Cycloalkylalkyl groups of (a).
6. The epoxy-modified polyurethane resin according to any one of claims 2 to 4, wherein m is preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
7. The epoxy-modified polyurethane resin according to claim 1, wherein the oxetane compound is selected from one or more of the following compounds:
8. the epoxy-modified polyurethane resin according to any one of claims 1 to 7, wherein M represents C 2 -C 100 Linear or branched alkylene of (2), wherein-CH 2 -is optionally substituted by-O-or-COO-; more preferably, M represents a residue formed by removing a terminal hydroxyl group from a polyether diol or a polyester diol, or by ring-opening via a terminal epoxy group and removing-O-; further preferably, the polyether diol is polyethylene glycol, polypropylene glycol, ethylene oxide-epoxyPropane copolymers or polytetrahydrofuran glycols;
preferably, R 1 Is represented by C 6 -C 18 Substituted or unsubstituted divalent aromatic radical of (1), C 5 -C 18 Substituted or unsubstituted divalent cycloalkyl radical of (A), C 2 -C 10 Substituted or unsubstituted divalent straight-chain alkyl group of (a); more preferably, R 1 Denotes the residue formed after removal of the-NCO group of the diisocyanate; further preferably, the diisocyanate is 2,4-TDI, 2,6-TDI, MDI, m-XDI, p-XDI, HDI, IPDI or HMDI.
9. A method for preparing the epoxy-modified polyurethane resin according to any one of claims 1 to 8, comprising the steps of:
providing a polyurethane resin body with a structure shown in a general formula I;
and carrying out grafting reaction on the polyurethane resin body and an oxetane compound to obtain the epoxy modified polyurethane resin.
10. The method according to claim 9, wherein the polyurethane resin body is prepared by the following method:
isocyanate is used as a first raw material, polyether diol or polyester diol is used as a second raw material, the first raw material and the second raw material are mixed, excess-NCO in the mixed raw material is controlled to be more than-OH, and polymerization reaction is carried out under the action of a catalyst to obtain the polyurethane resin body;
preferably, the mole ratio of-NCO to-OH in the mixed raw materials is (1.1-2) to 1;
preferably, the catalyst is an amine catalyst and/or an organometallic catalyst; more preferably, the amine catalyst is one or more selected from N, N-dimethylcyclohexylamine, triethylamine, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, triethanolamine and N, N' -dimethylpyridine, and the organic metal catalyst is an organic tin catalyst, and is further preferably dibutyltin dilaurate;
preferably, the catalyst is used in an amount of 0.01 to 1% by weight of the isocyanate;
preferably, the reaction temperature of the polymerization reaction is 30 to 120 ℃.
11. The method of claim 10, wherein the isocyanate is 2,4-TDI, 2,6-TDI, MDI, m-XDI, p-XDI, HDI, IPDI or HMDI; the polyether diol is polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer or polytetrahydrofuran diol.
12. The production method according to any one of claims 9 to 11, wherein during the grafting reaction, the active hydrogen functional group in the oxetane compound is in excess of the unreacted-NCO in the polyurethane resin bulk; preferably, the molar ratio of active hydrogen functional groups in the oxetane compound to unreacted-NCO in the polyurethane resin bulk is (1.1-2): 1.
13. The method of claim 12, wherein the reaction temperature during the grafting reaction is 50 to 80 ℃.
14. A curable resin composition comprising the epoxy-modified polyurethane resin of any one of claims 1 to 8 and an initiator.
15. Curable composition according to claim 14, characterized in that the initiator is a cationic initiator, preferably one or more of a diazonium salt, an onium salt and an organometallic complex.
16. The curable composition of claim 15, further comprising a cationically polymerizable compound; preferably, the cationic polymerizable compound includes one or more of epoxy compounds and vinyl ether compounds; more preferably, the epoxy compound is selected from one or more of bisphenol A epoxy resin, aliphatic glycidyl ether resin, aliphatic epoxy resin and oxetane compound, and the vinyl ether compound is selected from one or more of triethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether and dodecyl vinyl ether.
17. Use of the epoxy-modified polyurethane resin of any one of claims 1 to 8 or the curable composition of any one of claims 14 to 16 in an energy curable article, wherein the energy curable article is an ink, a coating or an adhesive.
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